Reactive dye mixture

ABSTRACT

A dye mixture comprises, as component (A), a reactive dye of the formula (A) wherein each of Y 1  and Y 2 , independently, is a vinyl group or a group of the formula —CH 2 CH 2 Q in which Q is a leaving group removable under alkaline conditions to provide a vinyl group; and, as component (B), at least one additional reactive dye selected from a monopyrazole dye of the formula (I), a mono or disazo dye of the formula (II), a monoazopyridone dye of the formula (III), a monoazonaphthyl dye of the formula (IV), a disazoaminonaphthyl dye of the formula (V), a formazan dye of the formula (VI), an azoacetoacetanalide dye of the formula (VII), a disazo dye of the formula (VIII), a naphthylamide or a naphthalenetriazole dye of the formula (IX), a metal phthalocyanine dye of the formula (X) or a triphendioxazine dye of the formula (XI), as defined herein.

[0001] This invention relates to mixtures of reactive dyes, inparticular to mixtures of reactive dyes containing, as one component, adisazo dye derived from H-acid.

[0002] As is well known, reactive dyes contain at least one substituentcapable of taking part in a reaction with a group present on a fabric tobe dyed during the dyeing operation.

[0003] EP-A-0149170 discloses a range of dyes of the formula

[0004] in which one X is hydrogen and the other sulpho, each of Y₁ andY₂ independently is a group —CH═CH₂, —CH₂CH₂OSO₃H, —CH₂CH₂SSO₃H,—CH₂CH₂Cl or —CH₂CH₂OR, and R is a low molecular weight alkanoyl,benzoyl or benzenesulphonyl group, optionally substituted by a C₁₋₄alkyl, C₁₋₄ alkoxy, halogen, carboxy or sulpho group.

[0005] A typical dye has the formula

[0006] EP-A-0149170 refers only to individual dyes, not mixturesthereof.

[0007] On the other hand, each of EP-A-0224224, EP-A-0679697,EP-A-0531968, EP-A-0668328 and EP-A-0600322 discloses respectivemixtures of dyes, one of which components is a disazo dye derived fromH-acid. One particular example of such a dye has the formula

[0008] This dye is available commercially as C.I. Reactive Black 5 andis added to other dyes as a dulling agent where appropriate.

[0009] We find surprisingly that the fastness of a dye mixture can beimproved if the dye mixture contains, as a component thereof, a dye ofthe formula (A)

[0010] wherein each of Y¹ and Y², independently, is a vinyl group or agroup of the formula —CH₂CH₂Q in which Q is a leaving group removableunder alkaline conditions to provide a vinyl group.

[0011] The dye mixture may contain, in addition to component (A), any ofa wide range of dyes.

[0012] More particularly, the present invention provides a dye mixturecomprising a reactive dye of the formula (A), given and defined above;and

[0013] at least one reactive dye (B) selected from

[0014] (I) a monoazopyrazole dye of the formula

[0015] wherein R¹ is an aryl group selected from phenyl and naphthylgroups optionally having at least one substituent thereon, thesubstituents, or each substituent independently, being selected from asulphonic acid group and a salt thereof, a C₁₋₄ alkyl group, a C₁₋₄alkoxy group, a hydroxy group, a carboxyl group, a chlorine atom, avinyl sulphonyl group and a group SO₂CH₂CH₂Q¹ in which Q¹ is a leavinggroup removable under alkaline conditions to provide a vinyl sulphonylgroup;

[0016] R² is a phenyl or naphthyl group, optionally having a least onesubstituent thereon, the substituent, or each substituent,independently, being selected from a sulphonic acid group and a saltthereof, a C₁₋₄ alkyl group, a C₁₋₄ alkoxy group, a hydroxy group, achlorine atom, a vinyl sulphonyl group, a group SO₂CH₂CH₂Q² in which Q²is a leaving group removable under alkaline conditions to provide avinyl sulphonyl group, a group Het and a group L⁵—Het, where Het is anoptionally substituted aromatic heterocyclic reactive or non-reactivegroup or a reactive or non-reactive group having an aliphatic chain andL⁵ is as defined below; and

[0017] R⁶ is a methyl group, an amide group or a carboxyl group or asalt thereof;

[0018] each of R⁴⁰ and R⁴¹, independently, is an aryl group selectedfrom phenyl and naphthyl groups, each of which, independently, isoptionally substituted by a vinylsulphonyl group, a group SO₂CH₂CH₂Q¹ inwhich Q¹ is a leaving group removable under alkaline conditions toprovide a vinylsulphonyl group; or the group Het, where Het is asdefined above;

[0019] at least one of R¹, R², R⁴⁰ and R⁴¹ being, or having thereon atleast one substituent which is, reactive;

[0020] each of L¹, L² and L⁵ independently is a linking group selectedfrom N(R²⁰), in which R²⁰ is hydrogen or C₁₋₄ alkyl; C(═O); C(═O)—O;S(═O)₂; S(═O)—NH; C(═O)—NH; and NHC(═O)NH; and

[0021] each of x, y and z, independently, is zero or 1; and, when thegroup R¹ is substituted by a hydroxy group ortho to the azo group, ametallized derivative thereof;

[0022] (II) a monoazo or disazo dye of the formula

[0023] wherein: Het is an optionally substituted aromatic heterocyclicreactive or non-reactive group or a reactive or non-reactive grouphaving an aliphatic chain;

[0024] R³ or each R³, independently, is a chlorine atom, a methyl group,a methoxy group, a sulphonic acid group or a salt thereof, or is anamino, group of the formula

[0025]  in which each of R¹⁸ and R¹⁹, independently, is hydrogen,chloro, methyl, (C₁₋₄ alkyl) carbonyl, aminocarbonyl, vinylsulphonyl ora group SO₂CH₂CH₂Q¹, in which Q¹ is as defined above;

[0026] R⁴, or each R⁴ independently, is hydrogen, a sulphonic acid groupor a salt thereof, a C₁₋₈ alkyl (preferably a C₁₋₄ alkyl) group, a C₁₋₄alkoxy group, a vinyl sulphonyl group or a group SO₂CH₂CH₂Q² in which Q²is a leaving group removable under alkaline conditions to provide avinyl sulphonyl group, which C₁₋₄ alkyl group or C₁₋₄ alkyl moiety ofthe C₁₋₄ alkoxy group is optionally interrupted by an oxygen atom toprovide an ether group and is optionally substituted by a vinylsulphonyl group or a group SO₂CH₂CH₂Q², in which Q² is as defined above;or R⁴ (or when q is 2, each R⁴ independently) is a phenyl groupoptitonally substituted by at least one sulphonic acid group or a saltthereof or at least one group Het, where Het is as defined above; or R⁴is a group Het, where Het is as defined above

[0027] R⁵ is an aryl group selected from phenyl and naphthyl groups eachoptionally substituted by at least one sulphonic acid group or, a saltthereof or at least one group Het, as defined above;

[0028] R²⁰ is a hydrogen atom or a C₁₋₄ alkyl group;

[0029] R²¹ is a hydrogen atom, a C₁₋₄ alkyl group, a sulphonic acid-C₁₋₄alkyl group, a chloroalkylsulphonyl-C₁₋₄ alkyl group or a group Het,where Het is as defined above;

[0030] m is 1 or 2;

[0031] p is zero, 1 or 2;

[0032] q is zero, 1 or 2;

[0033] each of w₁ and w₂ is zero or 1; and

[0034] w₃ is 1, 2 or 3; and

[0035] when p is zero, q is zero;

[0036] at least one of R⁴, R⁵, R¹⁸, R¹⁹, R²¹ and Het being, or havingthereon at least one substituent which is, reactive;

[0037] (III) a monoazopyridone dye of the formula

[0038] wherein: each of R⁴⁰, R⁴¹, L¹ and L² is as defined above;

[0039] R⁷ is optionally present and is a cyano group or the group—CH₂SO₃H or the group —C(═O)NH₂;

[0040] each of R²⁴ and R²⁵, irdependently, is a hydrogen atom, a C₁₋₄alkyl group, a sulpho-C₁₋₄ alkyl group, or a carboxyl group;

[0041] n is 1 or 2;

[0042] r is zero or 1; and

[0043] each of s₁ and s₂ is zero or 1; and when R⁴⁰ is a phenyl ornaphthyl group s₂ is 1;

[0044] at least one of R⁴⁰ and R⁴¹ being, or having thereon at least onesubstituent which is, reactive;

[0045] (IV) a monoazonaphthyl dye of the formula

[0046]  wherein:

[0047] each of R¹, R⁴⁰, R⁴¹, L¹, L², x, y and z is as defined above;

[0048] R⁹ is CH₃(C═O)—, Het (as defined above) or an aryl group selectedfrom phenyl and naphthyl, which Het or aryl group is optionallysubstituted by at least one substituent, the or each substituent,independently, being selected from a sulphonic acid group and a saltthereof, a C₁₋₄ alkyl group, a C₁₋₄ alkoxy group, a hydroxy group, anamino group optionally substituted by at least one methyl or sulphatogroup, a vinyl sulphonyl group and a group SO₂CH₂CH₂Q¹ in which Q¹ is asdefined above;

[0049] R³⁵ is a C₁₋₄ alkyl or C₂₋₄ alkenyl group, which C₁₋₄ alkyl orC₂₋₄ alkenyl group is optionally substituted by at least one halogenatom, a sulphonic acid group or salt thereof, a chloroalkylsulphonylgroup, a vinylsulphonyl group or —SO₂CH₂CH₂Q¹, where Q¹ is as definedabove and which C₁₋₄ alkyl or C₂₋₄ alkenyl group optionally additionallycontains at least one oxygen or sulphur atom in the chain thereof; thegroup Het (as defined above); or an aryl group selected from phenyl andnaphthyl, which Het or aryl group is optionally substituted by at leastone substituent, the substituent or each substituent independently,being selected from a sulphonic acid group and a salt thereof, a C₁₋₄alkyl group, a C₁₋₄ alkoxy group, a halogen atom, a hydroxy group, anamino group optionally substituted by at least one methyl or sulphatogroup, a vinylsulphonyl group, a vinylsulphonyloxyethyl group and agroup SO₂CH₂CH₂Q¹ in which Q¹ is as defined above;

[0050] R⁵⁰ is a vinylsulphonyl group or a group SO₂CH₂CH₂Q¹ (in which Q¹is as defined above);

[0051] at least one of R¹, R⁹, R³⁵, R⁴⁰, R⁴¹ and R⁵⁰ is, or has thereonat least one substituent which is, reactive;

[0052] L³ is a linking group selected from N(R²⁰), in which R²⁰ is asdefined above; CO; COO; NHCO; NHCOM; SO₂NH and SO₂;

[0053] L⁴ is a linking group selected from N(R²¹), in which R²¹ is asdefined above, CO, COO, NHCO, NHCONH, SO_(2,)N and SO₂;

[0054] Z is hydroxy, amino or methylamino;

[0055] a is zero or 1-4;

[0056] b is zero or 1-3;

[0057] c is zero or 1;

[0058] d is zero, 1 or 2;

[0059] e is zero or 1; and

[0060] when each of R¹ and Z provides a hydroxyl group ortho to the azogroup, a metallized derivative thereof;

[0061] (V) a disazoaminonaphthyl dye of the formula

[0062]  wherein:

[0063] each of R¹, R⁴⁰, R⁴¹, L¹, L², x, y and z is as defined above;

[0064] each of V and W, independently, is NH₂ or OH;

[0065] R¹⁴ is an aryl group selected from phenyl and naphthyl groupsoptionally having at least one substituent thereon, the substituents, oreach substituent independently, being selected from a sulphonic acidgroup and a salt thereof, a C₁₋₄ alkyl group, a C₁₋₄ alkoxy group, ahydroxy group, a vinyl sulphonyl group, a group SO₂CH₂CH₂Q¹ in which Q¹is a leaving group removable under alkaline conditions to provide avinyl sulphonyl group;

[0066] each of R⁵¹ and R⁵² independently is an aryl group selected fromphenyl and naphthyl groups each of which is optionally substituted by avinyl sulphonyl group, a group SO₂CH₂CH₂Q¹ in which Q¹ is a leavinggroup removable under alkaline conditions to provide a vinyl sulphonylgroup, or the group Het³, where Het³ is an optionally substitutedaromatic heterocyclic reactive group or a reactive group having analiphatic chain;

[0067] each of L³ and L⁴, independently, is a linking group selectedfrom N(R²⁰), in which R²⁰ is hydrogen or C₁₋₄ alkyl; C(═O); C(═O)—O;S(═O)₂; S(═O)—NH; C(═O)—NH; and NHC(═O)NH;

[0068] each of f, g and h, independently is zero or 1; and

[0069] at least one of R¹⁴, R⁴⁰, R⁴¹, R⁵¹ and R⁵² is, or has thereon atleast one substituent which is, reactive;

[0070] (VI) a formazan dye of the formula

[0071] wherein:

[0072] each of R¹⁶ and R¹⁷ independently of one another, each R¹⁶independently of one another and each R¹⁷ independently of one another,is a sulphonic acid group or a salt thereof, a vinyl sulphonyl group ora group SO₂CH₂CH₂Q¹ in which Q¹ is a leaving group removable underalkaline conditions to provide a vinyl sulphonyl group;

[0073] each of Het¹ and Het², independently, is an optionallysubstituted aromatic heterocyclic reactive or non-reactive group or areactive or non-reactive group having an aliphatic chain; and

[0074] each of R⁶⁰ and R⁶¹, independently, is an aryl group selectedfrom phenyl and naphthyl groups each of which is optionally substitutedby a sulphonic acid group or a salt thereof, a vinylsulphonyl group or agroup SO₂CH₂CH₂Q¹ in which Q¹ is as defined above;

[0075] X¹ is a sulphonic acid group or a salt thereof or halogen; eachof i, j and v, independently, is zero, 1 or 2; and each of k, 1, t andu, independently, is zero or 1; and

[0076] at least one of R¹⁶, R¹⁷, R⁵⁰, R⁵¹, Het¹ and Het² is, or hasthereon at least one substituent which is, reactive;

[0077] (VII) a dye of the formula

[0078] wherein: each of R¹, R², R³, R⁴, R²⁰, R²¹, R⁴⁰, L¹, Het, x, p, q,w₁, w₂ and w₃ is as defined above; and

[0079] at least one of R¹, R², R³ R⁴ R²¹, R⁴⁰ and Het is, or has thereonat least one substituent which is, reactive;

[0080] (VIII) a disazo dye of the formula

[0081] wherein

[0082] R⁵⁵ is an aryl group selected from phenyl and naphthyl groups;

[0083] R⁵⁶ is a sulphonic acid group or a salt thereof or a reactivegroup selected from a vinyl sulphonyl group and a group SO₂CH₂CH₂Q¹ inwhich Q¹ is a leaving group removable under alkaline conditions toprovide a vinyl sulphonyl group;

[0084] R⁵⁷ is an amino group or a group NHR^(A) in which R^(A) is a C₁₋₄alkyl group;

[0085] R⁵⁸ is a sulphonic acid group or a salt thereof;

[0086] R⁵⁹ is a sulphonic acid group or a salt thereof, a reactive groupselected from a vinyl sulphonyl group and a group SO₂CH₂CH₂Q² in whichQ² is a leaving group removable under alkaline conditions to provide avinyl sulphonyl group; or the group R⁵⁹ is a group Het or a groupL¹⁰-Het, where Het is an optionally substituted aromatic heterocyclicreactive or non-reactive group;

[0087] R⁶⁵ is a ureido group or a group HNC(═O)R^(B) in which R^(B) is aC₁₋₄ alkyl group;

[0088] L¹⁰ is a linking group selected from N(R²⁰), in which R²⁰ ishydrogen or C₁₋₄ alkyl; C(═O); C(═O)—O; S(═O)₂; S(═O)—NH; C(═O)—NH; andNHC(═O)NH;

[0089] y₁ is zero, 1, 2 or 3;

[0090] y₂ is zero, 1 or 2;

[0091] y₃ is zero or 1; and

[0092] y₄ is zero or 1; and at least one of R⁵⁶ and 59 is a reactivegroup.

[0093] (IX) a dye of the formula

[0094] (X) a metal phthalocyanine dye of the formula

[0095] wherein:

[0096] MPc is a metallophthalocyanine chromophore;

[0097] each of R⁷⁰ and R⁷¹ independently, is hydrogen or C₁₋₄ alkyl;

[0098] B is a hydrocarbon bridging group;

[0099] Het is a reactive heterocyclic group;

[0100] each of x₁, x₂ and x₃ is a respective average value;

[0101] x₁+x₂+x₃=4;

[0102] x₁ is at least 1

[0103] x₂ is zero or 1; and

[0104] x₃ is at least 1; and

[0105] (XI) a triphenodioxazine dye of the formula (XI) (or a saltthereof)

[0106] wherein: each of B¹ and B², independently, is a hydrocarbonbridging group; U¹ is H or SO₃H; and each of T¹ and T², independently,is halo, C₁₋₄ alkyl, or C₁₋₄ alkoxy; each of R⁸⁰ and R⁸¹ is a phenylgroup substituted by at least one sulphonic acid group or a saltthereof; each of Het¹ and Het² is as defined above; and

[0107] at least one of Het¹ and Het² is a reactive group.

[0108] Referring to the dye of the formula (A), preferably at least oneof Y¹ and Y² is the group —CH₂CH₂Q and Q is selected from chlorine,bromine, C₁₋₄-alkylsulfonyl, phenylsulfonyl, OSO₃H, SSO₃H, OP(O) (OH)₂,C₁₋₄-alkylsulfonyloxy, phenylsulfonyloxy, (C₁₋₄ alkyl) carbonyloxy,(C₁₋₄ dialkyl) amino or a radical of the formula

[0109] where Z⁹, Z¹⁰ and Z¹¹ are identical or different and are each,independently of one another, C₁₋₄ alkyl or benzyl and An^(θ) is in eachcase one equivalent of an anion. More preferably, each of Y¹ and Y² isthe group HO₃SOCH₂CH₂.

[0110] Referring now to the reactive dye (B), dyes in one preferredrange thereof contain a group Het, where Het is an optionallysubstituted aromatic heterocyclic reactive around derived from ahalogen-substituted heterocyclic compound selected from 1,3,5-triazine,quinoxaline, phthalazine, pyrimidine, pyridiazine and 2-(C₁₋₄alkylsulphonyl) benzothiazole. More preferably, the least onesubstituent is a halogen atom.

[0111] An alternative preferred range of reactive dyes (B) contains agroup Het, where Het is a reactive group having an aliphatic chain andselected from acryloyl, mono-, di- or trichloroacryloyl, mono-, di- ortri- bromoacryloyl, —CO—CCl═CH—COOH, —CO—CH═CCl—COOH, 2-chloropropionyl,1,2-dichloropropionyl, 1,2-dibromopropionyl, 3-phenylsulfonylpropionyl,3-methylsulfonylpropionyl, 2-sulfatoethylaminosulfonyl,2-chloro-2,3,3-trifluorocyclobutylcarbonyl,2,2,3,3-tetrafluorocyclobutylcarbonyl,2,2,3,3-tetrafluorocyclobutylsulfonyl,2-(2,2,3,3-tetrafluorocyclobutyl)acryloyl, 1- or 2-alkyl- or 1- or2-arylsulfonylacryloyl, or a radical of the formula SO₂—Y³ ₁, SO₂NH—Y³,CONH—L⁶—SO₂—Y³ or NHCONH—L⁶—SO₂—Y³ where L⁶ is C₁—C₄-alkylene orphenylene and Y³ is a vinyl group or a group of the formula CH₂CH₂Q³ inwhich Q³ is a leaving group removable under alkaline conditions toprovide a vinyl group.

[0112] It is also preferred that, the reactive dye (B) has at least oneof the groups Q¹ and Q² therein and the or each of groups Q¹ and Q²independently is selected from chlorine, bromine, C₁₋₄-alkylsulfonyl,phenylsulfonyl, OSO₃H, SSO₃H, OP(O)(OH)₂, C₁₋₄-alkylsulfonyloxy,phenylsulfonyloxy, (C₁₋₄ alkyl) carboxyloxy, (C₁₋₄ dialkyl) amino or aradical of the formula

[0113] where Z⁹, Z¹⁰ and Z¹¹ are identical or different and are each,independently of one another, C₁₋₄-alkyl or benzyl and An^(θ) is in eachcase one equivalent of an anion.

[0114] In a dye mixture wherein the reactive dye (B) is amonoazopyrazole dye of ,the formula (I), given and defined above, it ispreferred that at least one of the group[(R⁴¹—L²)_(z)(R⁴⁰—L¹)_(y)]_(x)R¹ and the group R² has at least onesulphonic acid group substituted thereon and at least the other of thegroup [(R⁴¹—L²)_(z)(R⁴⁰—L¹)_(y)]_(x)R¹ and the group R² has a group—SO₂CH₂SO₂Q² substituted thereon, Q² being as defined above.

[0115] In respective preferred ranges of the reactive dye (B) of theformula (I)

[0116] (i) x is zero and the group R¹ is substituted by at least one ofa sulphonic acid group and the group —SO₂CH₂SO₂Q¹, wherein Q¹ is asdefined above;

[0117] (ii) each of x, y and z is 1, each of L¹ and L² is NH, R⁴⁰ is thegroup Het, where Het is a triazine ring substituted by a halogen atomand R⁴¹ is an optionally substituted phenyl group.

[0118] (iii) each of x and z is 1, y is zero, L² is NH and R⁴¹ is thegroup Het, where Het is a difluorochloropyrimidinyl group; and

[0119] (iv) each of x and z is 1, y is zero, L² is CONH (in which thenitrogen atom is attached to the group R¹ and the carbon to the groupR⁴¹) and R⁴¹ is the group Het, where Het is a 2,3-dichloroquinoxalinegroup.

[0120] In a reactive dye (B) of the formula (I), R² is preferably aphenyl or naphthyl group substituted by

[0121] (i) at least one of a sulphonic acid group and the group—SO₂CH₂SO₂Q², where Q² is as defined in claim 1; or

[0122] (ii) at least by the group NH-Het, where Het is a is triazinering substituted by a halogen atom and optionally substituted by thegroup

[0123] In a reactive dye (B) of the formula (I), the group R¹ may besubstituted by a hydroxy group ortho to the azo group and the reactivedye (B) may then be in the form of a copper complex.

[0124] Reference is now made to a dye mixture wherein the reactive dye(B) is monoazo or disazo dye of the formula (II), given and definedabove.

[0125] In such a mixture it is preferred that in the reactive dye (B) ofthe formula (II), when m is 1 and R⁴ is alkyl, R⁴ is C₁₋₄ alkyl.

[0126] It is also preferred that the group R⁵ is an aryl group selectedfrom phenyl and naphthyl groups each substituted by at least onesulphopic acid group or a salt thereof or by a group Het, wherein Het isa vinylsulphonyl group or a group SO₂CH₂CH₂Q¹ in which Q¹ is as definedabove.

[0127] In an especially preferred reactive dye (B) of the formula (II),m is 1, so that the dye is a monoazo dye.

[0128] In preferred ranges of monoazo dyes (B) of the formula (II) in amixture in accordance with the invention,

[0129] (i) each of w₁, w₂, p and q is zero, w₃ is at least 2, at leastone of the groups R³ is a sulphonic acid group and the group R⁵ is anaryl group selected from phenyl and naphthyl groups each substituted bya vinylsulphonyl group or a group —SO₂CH₂CH₂Q¹, where Q¹ is as definedabove.

[0130] (ii) each of w₁ and w₂ is zero, each of p and q is 1, R²¹ ishydrogen and R⁴ is selected from a triazine ring substituted by at leastone halogen atom and optionally additionally substituted by an aminogroup; and a pyrimidine group substituted by at least one halogen atomand optionally additionally substituted by a methyl group;

[0131] (iii) each of w₁, w₂, p and q is 1, R²⁰ is hydrogen, Het is atriazine ring substituted by a halogen atom, R²¹ is hydrogen and R⁴ isselected from a phenyl group or a group —SO₂CH₂CH₂Q¹, where Q¹ is asdefined above, and a straight or branched C₂₋₄ alkylene chainsubstituted by a substituent selected from a hydroxyl group; a sulphonicacid group or salt thereof; a vinylsulphonyl group, a group—SO₂CH₂CH₂Q², where Q² is as defined above; and a pyrimidinylamino groupin which the pyrimidinyl group is substituted by at least one halogenatom and optionally additionally by a methyl group; and which straightor branched C₂₋₄ alkylene group optionally contains a hetero atomselected from O, S and N(H);

[0132] (iv) each of w₁ and w₂ is zero, each of p and q is 1 and each ofR²¹ and R⁴ is the group OSO₃H; and

[0133] (v) w₁ is zero, w₂ is 1, p is 1, q is 1, R²¹ is hydrogen, R⁴is apyrimidinyl group substituted by at least one halogen atom andoptionally additionally substituted by a methyl group and Het is anon-reactive heterocyclic group of the formula

[0134] An especially preferred dye mixture contains a dye of the formula(44) as the reactive dye (B) of formula (II)

[0135] Reference is now made to a dye mixture wherein the reactive dye(B) is a monoazopyridone dye of the formula (III), given and definedabove.

[0136] In respective preferred ranges of the reactive dye (B) of theformula (III),

[0137] (i) each of r, s₁ and s₂ is 1, each of L¹ and L² is NH, R⁴⁰ is atriazine ring substituted by a halogen atom and R⁴¹ is selected from aphenyl group substituted by at least one of a chlorine atom, a sulphonicacid group or a salt thereof, a vinylsulphonyl group or a group—SO₂CH₂CH₂Q¹, where Q¹ is as defined above; and a straight or branchedchain C₂₋₄ alkylene group optionally containing at least one oxygen atomand substituted by a vinylsulphonyl group or a group —SO₂CH₂CH₂Q¹, whereQ¹ is as defined above;

[0138] (ii) each of r and s₁ is 1, s₂ is zero, L² is NH, R⁴¹ is apyrimidinyl group substituted by at least one halogen atom andoptionally additionally substituted by a methyl group and R⁴⁰ is anaphtho-(1,2-d)-1,2,3-triazole substituted by at least one sulphonicacid group or salt thereof; and

[0139] (iii) each of r₁, s₁ and s₂ is 1, L¹ is CONH (in which the carbonatom is attached to the group R⁴⁰), L² is NH, R⁴⁰ is an optionallysubstituted phenyl group and R⁴¹ is a pyrimidinyl group substituted byat least one halogen atom and optionally additionally substituted by amethyl group.

[0140] Reference is now made to a dye mixture wherein the reactive dye(B) is a monoazonaphthyl dye of the formula (IV), given and definedabove.

[0141] In one preferred range of such dyes,

[0142] (i) x is zero, d is 1 and a or b is 1. More preferably e is zero.

[0143] In other preferred respective ranges,

[0144] (ii) x is 1, y is zero, z is 1, L² is NH and R⁴¹ is a pyrimidinylgroup substituted by at least one halogen atom and optionallyadditionally substituted by a methyl group;

[0145] (iii) x is 1, y is zero, z is 1, L² is CONH (with the carbon atomattached to the group R¹ and the nitrogen atom to the group R⁴¹) and R⁴¹is a phenyl group substituted by a vinylsulphonyl group or a group—SO₂CH₂CH₂Q¹, where Q¹ is as defined above; and

[0146] (iv) each of x, y and z is 1, each of L¹ and L² is NH, R⁴⁰ is atriazine ring substituted by a halogen atom and R⁴¹ is an aromatic groupselected from phenyl and naphthyl groups each substituted by at leastone of a sulphonic acid group or a salt thereof, a vinylsulphonyl groupand the group —SO₂CH₂CH₂Q¹, where Q¹ is as defined above.

[0147] In such ranges (ii)-(iv) of dyes (B) of the formula (IV), morepreferably, e is zero.

[0148] In other preferred ranges of the reactive dye (B) of the formula(IV),

[0149] (v) e is 1, c is zero, L³ is CONH (where either the nitrogen orcarbon atom thereof is attached to the group R⁹) and R⁹ is a methylgroup;

[0150] (vi) e is 1, c is zero, L³ is CONH (where either the nitrogen orcarbon atom thereof is attached to the group R⁹) and R⁹ is a phenylgroup optionally substituted by at least one substituent, the or eachsubstituent being selected from methoxy, carboxyethyl, sulphoethyl,carboxyethenyl, 1,2-dibromoalkyl, chloroethylsulphonyl, vinylsulphonyl,a group of the formula —SO₂CH₂CH₂Q¹, where Q¹ is as defined above and a2,3-dichloroquinoxaline group.

[0151] (vii) e is 1, c is 1, L³ is CONH (where either the nitrogen orcarbon atom thereof is attached to the group R⁹), R⁹ is a phenyl groupsubstituted at least by the group L⁴—R³⁵, where L⁴ is NH and R³⁵ is avinyl group optionally substituted by a halogen atom or a pyrimidinylgroup substituted by a halogen atom and optionally additionallysubstituted by a methyl group; and

[0152] (viii) e is 1, c is zero, L³ is N(R²⁰), where R²⁰ is as definedabove (and is more preferably a hydrogen atom or a methyl group) and R⁹is a vinylsulphonyl group, a group —SO₂CH₂CH₂Q¹ wherein Q¹ is as definedin claim 1, or a pyrimidinyl group substituted by a halogen atom andoptionally additionally substituted by a methyl group.

[0153] In yet another preferred range

[0154] (ix) e is 1, c is zero, L³ is N(R²⁰), where R²⁰ is as definedabove and R⁹ is a triazine ring substituted by at least one halogenatom. In this range the triazine ring is preferably substituted by twohalogen atoms or by one halogen atom and a morpholinyl group.

[0155] In another preferred range,

[0156] (x) e is 1, C is 1, L³ is N(R²⁰), where R²⁰ is as defined above,L⁴ is the group R²¹, where R²¹ is as defined above, and R³⁵ is selectedfrom a phenyl group optionally substituted by a sulphonic acid group orsalt thereof, a halogen atom, a vinylsulphonyloxyalkyl group, avinylsulphonyl group or the group —SO₂CH₂CH₂Q¹, where Q¹ is as definedabove; and a C₁₋₄ alkyl group optionally substituted by a vinylsulphonylgroup, the group —SO₂CH₂CH₂Q¹ where Q¹ is as defined above, a sulphonicacid group or a salt thereof or a chloroalkylsulphonyl group, which C₁₋₄alkyl group optionally additionally contains at least one oxygen orsulphur atom in the chain thereof

[0157] In dye mixtures containing a reactive dye (B) of the formula (IV)within the above ranges x is preferably zero.

[0158] In the reactive dye (B) of the formula (IV), each of the groupsR¹ and the naphthalene nucleus may be substituted by a respectivehydroxyl group ortho to the azo group and the reactive dye (B) may thenbe in the form of a copper complex thereon.

[0159] An especially preferred dye mixture contains a dye of the formula(53) as the reactive dye (B)

[0160] Reference is now made to a dye mixture wherein the reactive dye(B) is a disazo dye of the formula (V), given and defined above. In suchdyes, the respective sulphonic acid groups on the naphthalene nucleusare preferably in the 3- and 6- positions (i.e. such dyes are preferablyderived from H-acid).

[0161] In one preferred range of dyes of the formula

[0162] (i) V is amino, W is hydroxy, each of R¹ and R¹⁴ is a phenylgroup substituted by at least one substituent, the or each substituentindependently being selected from a sulphonic acid group or a saltthereof, a vinyl sulphonyl group and a group SO₂CH₂CH₂Q¹, where Q¹ is asdefined above and R¹⁴ is optionally additionally substituted by at leastone methoxy group.

[0163] It is also preferred, especially for one sub-range within therange (i), that each of x and h is zero. Such a range of dyes includesthose of the formula (A) and a mixture in accordance with the inventionmay indeed contain only dyes of the formula (A), one such dye of themixture being regarded as a dye of the formula (A) and at least oneother such dye of the mixture being regarded as a dye of the formula(V).

[0164] In an alternative preferred range of dyes of the formula (V),especially for another sub-range within the range (i), at least one of xand h is 1 and more preferably each of x and h is 1.

[0165] In a preferred sub-range (ii) of dyes (B) of the formula (V),within the range (i), x, y and z is 1, each of L¹ and L² is NH, R⁴⁰ is atriazine ring substituted by a halogen atom and R⁴¹ is a phenyl groupsubstituted by at least one substituent, the or each substituentindependently being selected from a sulphonic acid group or a saltthereof, a vinylsulphonyl group and a group SO₂CH₂CH₂Q¹, where Q¹ is asdefined above.

[0166] In the preferred ranges (i) and (ii) above, more preferably, eachof f, g and h is 1, each of L³ and L⁴ is NH, R⁵¹ is a triazine ringsubstituted by a halogen atom and R⁵² is a phenyl group substituted byat least one substituent the or each substituent independently beingselected from a halogen atom, a sulphonic acid group or a salt thereof,a vinylsulphonyl group and a group SO₂CH₂CH₂Q¹, where Q¹ is as definedabove.

[0167] In a preferred range (iii) of reactive dyes (B) of the formula(V), V is amino, W is hydroxy, h is zero and R¹⁴ is a naphthaalene groupsubstituted by at least one sulphonic acid group. More preferably, inthis range (iii), each of x, y and z is 1, R¹ is a phenyl groupoptionally substituted by a sulphonic acid group or a salt thereof, eachof L¹ and L² is NH, R⁴⁰ is a triazine ring substituted by a halogen atomand R⁴¹ is a phenyl group substituted by at least one substituent, theor each substituent independently being selected from a sulphonic acidgroup or a salt thereof, a vinylsulphonyl group and a group SO₂CH₂CH₂Q¹,where Q¹ is as defined above.

[0168] In a preferred range (iv) of the reactive dyes (B) of the formula(V), V is amino, W is hydroxy, h is 1, f is zero, g is 1, L⁴ is NH andR⁵² is the group Het³, where Het³ is a substituted aromatic heterocyclicgroup. In this range (iv), more preferably the group Het³ is apyrimidinyl group substituted by at least one halogen atom andoptionally additionally substituted by a methyl group and still morepreferably x is zero and R¹ is a phenyl group substituted by avinylsulphonyl group or SO₂CH₂CH₂Q¹, where Q¹ is as defined above.

[0169] In a preferred range (v) of the reactive dyes (B) of the formula(V), V is amino, W is hydroxy, h is 1, f is zero, g is 1, L⁴ is NHCO(where either the nitrogen or carbon atom thereof is attached to thegroup R¹⁴) and R⁵² is the group Het³, where Het³ is a reactive grouphaving an aliphatic chain. More preferably, in this range (v), the groupHet³ is a vinylsulphonyl group or SO₂CH₂CH₂Q¹, where Q¹ is as definedabove and still more preferably x is zero and R¹ is a phenyl groupsubstituted by a vinylsulphonyl group or SO₂CH₂CH₂Q₁, where Q¹ is asdefined above.

[0170] One especially preferred dye mixture contains a dye of theformula (105) as a dye of the formula (V)

[0171] and more preferably additionally contains a dye of the formula(44) as another dye (B), of the formula (II)

[0172] Another especially preferred dye mixture contains at least oneand more preferably both of the dyes of the formulae (163) and (167)

[0173] Reference is now made to a dye mixture wherein the reactive dye(B) is a formazan dye of the formula (VI), given and defined above.

[0174] In preferred respective ranges of the reactive dye (B) of theformula (VI)

[0175] (i) each of u and v is zero, i is 1, R¹⁶ is a sulphonic acidgroup or a salt thereof, j is 2 and one R¹⁷ is a sulphonic acid group ora salt thereof and the other R¹⁷ is a vinylsulphonyl group orSO₂CH₂CH₂Q¹, where Q¹ is as defined above; and

[0176] (ii) v is zero, i is 1, R¹⁶ is a sulphonic acid group or a saltthereof, j is 1, R¹⁷ is a sulphonic acid group, u is 1 and Het¹ is atriazine ring substituted by a halogen atom. In one preferred sub-rangewithin the range (ii), each of k and l is zero, t is 1 and R⁶¹ is aphenyl group substituted by at least one sulphonic acid group or a saltthereof, while in another preferred sub-range with the range (ii), eachof k, 1 and t is 1, each of R⁶⁰ and R⁶¹ independently is a phenyl groupsubstituted by at least one sulphonic acid group or a salt thereof andHet² is a triazine ring substituted by a halogen atom. In yet anotherpreferred sub-range within the range (ii), each of k and t is zero, l is1 and Het² is a reactive group having an aliphatic chain.

[0177] Reference is now made to a dye mixture wherein the reactive dye(B) is a dye of the formula (VII), given and defined above.

[0178] In one preferred range of such dyes, x is zero and each of p, q,w and w₂ is 1. More preferably, in such a range, R¹ is a naphthalenering substituted by at least one sulphonic acid group. It is alsopreferred that, in such a range, w₃ is 1 and R³ is a methoxy group.Moreover, a preferred group of R²⁰ is hydrogen and preferred groups ofR²¹ are hydrogen, methyl and ethyl. A preferred group R⁴ is a phenylgroup substituted by at least one sulphonic acid group.

[0179] In another preferred range of such dyes (VII), each of p, q, w₁and w₂ is zero. More preferably, in such a range, w₃ is 3 and at leastone of R³ is a sulphonic acid group. Other groups of R³ are preferablymethyl, methoxy, amino or further sulphonic acid groups. It is alsopreferred that where, in such dyes, x is 1, R¹ is a phenyl or naphthylgroup substituted by at least one sulphonic acid group, L¹ is NH and R⁴⁰is a reactive halopyrimidine group, especially a group containing atleast one, more especially at least two fluorine atoms and particularlya difluorochloropyrimidine group, and that where, in such dyes x iszero, R¹ is a phenyl groups substituted by a vinyl sulphonyl group orSO₂CH₂CH₂Q¹, where Q¹ is as defined above and optionally additionallysubstituted by at least one methoxy group.

[0180] Reference is now made to a dye mixture wherein the reactive dye(B) is a disazo dye of the formula (VIII), given and defined above.

[0181] In one preferred range of such dyes,

[0182] R⁵⁵ is a naphthyl group;

[0183] R⁵⁶ is a sulphonic acid group or a salt thereof;

[0184] R⁵⁹ is a group L¹⁰-Het, where L¹⁰ is the group N(H)— and Het is areactive heterocyclic group substituted by at least one halogen atom;

[0185] y₁ is 1, 2 or 3; and

[0186] each of y₂, y₃ and y₄ is zero.

[0187] A particularly preferred such disazo dye of the formula (VIII) ina dye mixture embodying the invention has the formula

[0188] In another preferred range of such dyes of the formula (VIII)

[0189] R⁵⁵ is a phenyl group;

[0190] the group R⁵⁶ or each group R⁵⁶ independently is a sulphonic acidgroup or a salt thereof or is a reactive group selected from a vinylsulphonyl group and a group SO₂CH₂CH₂Q² in which Q² is as defined above;

[0191] y₁ is 1 or 2; and

[0192] at least one group R⁵⁶ is a said reactive group or the group R⁵⁹is or includes a reactive group.

[0193] More preferably, at least one group R⁵⁶ or the group R⁵⁹ is areactive group selected from a vinyl sulphonyl group and a groupSO₂CH₂CH₂Q² in which Q² is as defined above; or at least one group R⁵⁶is a sulphonic acid group or a salt thereof and R⁵⁹ is the groupL¹⁰-Het, where L¹⁰ is the group N(H)— and Het is a reactive triazinegroup substituted by a halogen atom and additionally by the groupNHCH₂CH₂SO₃H.

[0194] Especially preferred dyes have the formulae

[0195] Reference is now made to a dye mixture wherein the reactive dye(B) is a phthalocyanine dye of the formula (X), given and defined above.

[0196] Preferably, in the reactive dye (B) of the formula (X),respective average values of x₁, x₂ and x₃ are x₁ is 3, x₂ is zero andX₃ as 1, three of the four isoindole rings of the phthalocyanine have arespective sulphonic acid substituent (or a salt thereof) thereon andthe other isoindole ring has a group SO₂NH—B—NH-Het substituted thereon.More preferably B is a straight or branched C₂₋₄ alkylene group and Hetis a triazine ring substituted by at least one halogen atom andoptionally additionally substituted by a methoxy group.

[0197] Reference is now made to a dye mixture wherein the reactive dye(B) is a triphendioxazine dye of the formula (XI), given and definedabove, or a salt thereof.

[0198] Preferably, in such a reactive dye (B) of the formula (XI), eachof T¹ and T² is a halogen atom, each U¹ is a sulphonic acid group or asalt thereof, each of B¹ and B² independently is a straight or branchedC₂₋₄ alkylene group, each of Het¹ and Het² independently is a triazinering substituted by a halogen atom and each of R⁸⁰ and R⁸¹ independentlyis a phenyl group substituted by at least one sulphonic acid group or asalt thereof.

[0199] The dyes of the formula (A) can be prepared by diazotising eachof the amines (XX) and (XXI)

[0200] wherein each of y¹ and y² is as defined above and firstlycoupling the diazotised amine (XXI) under strongly acid conditions (pH1-2) to H-acid to provide an azo group ortho to the amine group andthereafter coupling the diazotised amine (XX) under slightly acidic,neutral or alkaline conditions (pH 6-7) to the H-acid to provide an azogroup ortho to the hydroxy group.

[0201] The diazotisalion reactions may each be carried out by adjustingthe pH of the amine with a buffer to about 5.3-6, adding an aqueoussolution of hydrochloric acid and ice to cool to 0-5° C. and then addinga sodium nitrite solution.

[0202] The coupling reactions may each be carried out by adjusting thepH as described above and allowing reaction to take place at atemperature of from 4 to 8° C. for at least 3 hours.

[0203] These and other methods of preparing the dyes of the formula (A)are described in EP-A-0149170.

[0204] Likewise disazo dyes (B) of the formula (V) may be prepared in ananalogous manner. Methods of preparation of such dyes are also disclosedin DE-A-3875658 and DE-A-3622080.

[0205] Dyes (B) of the formula (I) may be prepared by the methodsdisclosed in DE-A-3717667.

[0206] Dyes (B) of the formula (II) may be prepared by the methoddisclosed in DE-A-3927790, DE-A-3515651 and EP-A-0761768.

[0207] Dyes (B) of the formula (III) may be prepared by the methodsdisclosed in U.S. Pat. No. 4,618,671, DE-A-3717814 and DE-A-3829595.

[0208] Dyes (B) of the formula (IV) may be prepared by the methoddisclosed in U.S. Pat. No. 4,841,031, EP-A-0343262 and EP-B-0776947.

[0209] Dyes (B) of the formula (VI) may be prepared by the methodsdisclosed in DE-A-3737536, DE-A-3743236 and DE-A-3840653.

[0210] Dyes (B) of the formula (X) may be prepared by the methodsdisclosed in WO-A-98/49240.

[0211] Dyes (B) of the formula (XI) may be prepared by the methodsdisclosed in DE-A-3423581 and EP-A-0773264.

[0212] Examples of dyes (B) of the formula (VII) are CI Reactive Yellow57, CI Reactive Yellow 106, CI Reactive Yellow 160 and CI ReactiveYellow 167, all commercially available.

[0213] A preferred dye mixture in accordance with the inventioncomprises, by weight of the total weight of the dyes, from 10-99.5% byweight, inclusive of component (A), given and defined above, and from0.5 to 90% by weight inclusive of component (B), given and definedabove. Respective progressively more preferred ranges are as follows:

[0214] 10-99% by weight, inclusive of component (A) and from 1 to 90% byweight, inclusive of component (B);

[0215] from 10-98.5% by weight, inclusive, of component (A) and from1.5-90% by weight, inclusive, of component (B);

[0216] from 10-97% by weight, inclusive, of component (A) and from 3-90%by weight, inclusive, of component (B);

[0217] from 10-95% by weight, inclusive, of component (A) and from 5-90%by weight, inclusive, of component (B);

[0218] from 10-90% by weight, inclusive, of component (A) and from10-90% by weight, inclusive, of component (B);

[0219] from 15-90% by weight, inclusive, of component (A); from 10-85%by weight, inclusive, of component (B);

[0220] from 20-90% by weight, inclusive, of component (A) and from10-80% by weight, inclusive, of component (B);

[0221] from 30-90% by weight, inclusive, of component (A) and from10-70% by weight, inclusive, of component (B); and

[0222] In an especially preferred mixture, component (B) is a mixture ofdyes (B).

[0223] Mixtures embodying the invention can be prepared by merely mixingthe individual dyes or, in some cases, by synthesis using a mixture ofdiazotising components. This method is especially suitable whencomponent (B) is at least one dye of the formula (V). The dye mixturemay be isolated, for example, by spray drying or salting out.

[0224] The mixtures can be used to dye or print on substrates containinga hydroxyl group or nitrogen atom, for example, silk, leather, wool,polyamides, polyurethanes and cellulosic materials, especially cotton.

[0225] The mixtures provide excellent properties including resistance tomodern peroxide based detergents, fastness to repeat washing, good lightfastness, excellent wash-off, good build-up, good compatibility of thedyes with one another and a robustness to process variables.

[0226] The reactive dye (A) alone gives a navy shade on cotton and maybe mixed with at least one yellow, orange, red or blue reactive dye (B)to give a forest green, navy, brown or black shade.

[0227] The mixtures have outstanding properties in comparison with knownmixtures, for example CI Reactive Black 5, referred to above, which isoften used in a mixture with other dyes as a dulling agent.

[0228] Preferred embodiments of the invention will now be described inmore detail with reference to the following Examples, in which thenumbers assigned to the dyes are those given in Table 2 and all partsare by weight unless otherwise stated. In the Examples, dye A has theformula

EXAMPLE 1

[0229] 75 parts of dye (A)¹, 20 parts of dye (167) and 5 parts of dye(163) were mixed. The mixture was used to dye cotton, by application ofcold pad batch and warm exhaust (40, 50 or 60° C.) techniques asdescribed below, in a navy shade resulting in good light fastness andfastness to repeated washing.

[0230] Exhaust Application

[0231] 100 g of cotton fabric were dyed in a dyebath that contained 1000ml water, 12 g of the mixture of Example 1, 2.5 g sodium carbonate, 1 g32 weight % sodium hydroxide solution and 60 g sodium sulphatedecahydrate. The dyeing was started at 30° C., the temperature wasraised to 50° C. over a period of 30 minutes and the dyeing wascontinued for a further 60 minutes at this temperature. After cooling toroom temperature the dyeing was rinsed and boiled with detergent, anddried.

[0232] Cold Pad-batch Application

[0233] At room temperature woven cotton fabric was soaked in a padderwith dye liquor that contained per 1000 g dye liquor 60 g of dye mixtureof Example 1, 50 g sodium silicate (38° B'e) and 30 g 32 weight % sodiumhydroxide solution. After 70% pick-up the paddings are rolled andcovered with cling film. After storing for 8 h at room temperature thepaddings are removed from the cling film, rinsed in cold water, hotrinsed with detergent, and dried.

EXAMPLE 2

[0234] 60 parts of dye (A), 24 parts of dye (44) and 16 parts of dye(105) were mixed mechanically. The dye mixture was applied to cottonusing the application and fixing methods of Example 1, resulting in ablack shade providing outstanding fastness properties.

EXAMPLE 3

[0235] Dye (A)¹ and dye (53) were synthesised separately according toknown procedures. 65 parts of reaction solution of dye (A)¹ and 35 partsof reaction solution of dye (53) were mixed and the dye mixture wasisolated by spray drying. The dye mixture was applied to cotton usingthe application and fixing methods of Example 1, resulting in a blackshade providing outstanding fastness properties.

[0236] Further examples were made achieving the same outstandingfastness properties and these are given in Table 1: TABLE 1 Parts YellowParts Red Dye Parts Orange Parts Example dye (A) Dye No. Yellow Dye No.Red dye Dye No. Orange dye 4 60 10 20 126 20 5 58 14 25 127 17 6 65 2314 121 21 7 55 44 25 129 20 8 70 49 15 91 15 9 65 15 10 105 25 10 67 5533 11 62 61 38 12 60 69 40

[0237] Still further (binary mixture) examples were made and whenapplied via the cold pad-batch application method of Example 1 achievedthe same outstanding fastness properties, as shown in Table 2. TABLE 2Parts Yellow/Orange Yellow/Orange Example Parts dye (A) Dye No. dye 1517 10 4 16 34 10 7 17 17 49 3 18 34 49 6 19 17 44 3 20 34 44 6 21 17 237 22 34 23 14 23 17 61 3 24 34 61 6 25 17 53 2.4 26 34 53 6 27 17 67 328 34 67 6 29 17   85A 2 30 34   85A 4 31 17    85B 3 32 34    85B 6

EXAMPLE 13

[0238] 100 g of cotton fabric was dyed according to the proceduresdescribed for Example 1 using 3 g of a dye mixture containing 1.5 g dye(A)¹, 0.6 g dye (1), 0.3 g dye (2) and 0.57 g dye (94) resulting in abrown shade providing outstanding fastness properties.

EXAMPLE 14

[0239] 100 g of cotton fabric was dyed in a dyebath that contained 1000ml water, 3 g of a mixture containing 1.4 g dye (A)¹, 0.13 g dye (150),0.54 g dye (15), 0.30 g dye (69), 0.28 g dye (90) and 0.35 g dye (101),15 g sodium carbonate and 60 g sodium chloride. Dyeing was started at40° C., the temperature was raised to 60° C. over a period of 20 minutesand dyeing was continued for a further 60 minutes at this temperature.After cooling to room temperature the dyeing was rinsed and boiled withdetergent resulting in a brown shade providing outstanding fastnessproperties.

[0240] For each of the dyes shown in Table 2 below, dye mixtures may beapplied according to any of the procedures described in Examples 1 and14 or by similar application methods Lo achieve outstanding fastnessproperties. No. Dyes Colour on cotton 1

yellow 2

yellow 3

yellow 4

yellow 5

yellow 6

yellow 7

golden yellow 8

yellow 9

yellow 10

yellow 11

yellow 12

golden yellow 13

golden yellow 14

yellow 15

yellow 16

golden yellow 17

yellow 18

yellow 19

golden yellow 20

yellow 21

yellow 22

golden yellow 23

yellow 24

yellow 25

yellow 26

yellow 27

yellow 28

yellow 29

golden yellow 30

yellow 31

golden yellow 32

golden yellow 33

yellow 34

yellow 35

yellow 36

yellow 37

yellow 38

yellow 39

yellow 40

yellow 41

golden yellow 42

yellow 43

yellow 44

yellow 45

yellow 46

golden yellow 47

yellow 48

yellow 49

yellow 50

yellow 51

yellow 52

orange 53

orange 54

orange 55

orange 56

orange 57

orange 58

orange 59

orange 60

orange 61

orange 62

orange 63

orange 64

orange 65

orange 66

orange 67

orange 68

orange 69

orange 70

orange 71

orange 72

orange 73

orange 74

orange 75

orange 76

orange 77

orange 78

orange 79

orange 80

orange 81

orange 82

orange 83

orange 84

orange 85

orange 85A

ORANGE 85B

ORANGE 86

red 87

red 88

red 89

red 90

red 91

red 92

red 93

red 94

red 95

red 96

red 97

red 98

red 99

red 100

red 101

red 102

red 103

red 104

red 105

red 106

red 107

red 108

red 109

red 110

red 111

red 112

bluish red 113

red 114

red 115

red 116

red 117

red 118

red 119

red 120

red 121

red 122

red 123

red 124

red 125

red 126

red 127

red 128

red 129

red 130

red 131

red 132

red 133

red 134

red 135

red 136

red 137

red 138

red 139

red 140

red 141

red 142

red 143

red 144

red 145

red 146

blue 147

turquoise 148

navy 149

navy 150

blue 151

navy 152

blue 153

blue 154

navy 155

navy 156

navy 157

blue 158

navy 159

navy 160

blue 161

navy 162

navy 163

navy 164

navy 165

navy 166

navy 167

navy 168

orange 169

yellow 170

yellow 171

orange

1. A dye mixture comprising, as component (A), a reactive dye of theformula (A)

wherein each of Y¹ and Y², independently, is a vinyl group or a group ofthe formula —CH₂CH₂Q in which Q is a leaving group removable underalkaline conditions to provide a vinyl group; and, as component (B), atleast one of reactive dye selected from (I) a monoazopyrazole dye-of theformula

wherein: R¹ is an aryl group selected from phenyl and naphthyl groupsoptionally having at least one substituent thereon, the substituents, oreach substituent independently, being selected from a sulphonic acidgroup and a salt thereof, a C₁₋₄ alkyl group, a C₁₋₄alkoxy group, ahydroxy group, a carboxyl group, a chlorine atom, a vinyl sulphonylgroup and a group SO₂CH₂CH₂Q¹ in which Q¹ is a leaving group removableunder alkaline conditions to provide a vinyl sulphonyl group; R² is aphenyl or naphthyl group, optionally having at least one substituentthereon, the substituent, or each substituent, independently, beingselected from a sulphonic acid group and a salt thereof, a C₁₋₄alkylgroup, a C₁₋₄alkoxy group, a hydroxy group, a chlorine atom, a vinylsulphonyl group, a group SO₂CH₂CH₂Q² in which Q² is a leaving groupremovable under alkaline conditions to provide a vinyl sulphonyl group,a group Het and a group L⁵-Het, where Het is an optionally substitutedaromatic heterocyclic reactive or non-reactive group or a reactive ornon-reactive group having an aliphatic chain and L⁵ is as defined below;and R⁶ is a methyl group, an amide group or a carboxyl group or a saltthereof; each of R⁴⁰ and R⁴¹, independently, is an aryl group selectedfrom phenyl and naphthyl groups, each of which, independently, isoptionally substituted by a vinylsulphonyl group, a group SO₂CH₂CH₂Q¹ inwhich Q¹ is a leaving group removable under alkaline conditions toprovide a vinylsulphonyl group; or the group Het, where Het is asdefined above; at least one of R¹, R², R⁴⁰ and R⁴¹ being, or havingthereon at least one substituent which is, reactive; each of L¹ L² andL⁵ independently is a linking group selected from N(R²⁰), in which R²⁰is hydrogen or C₁₋₄ alkyl; C(═O); C(═O)—O; S(═O)₂; S(═O)—NH; C(═O)—NH;and NHC(═O)NH; and each of x, y and z, independently, is zero or 1; and,when the group R¹ is substituted by a hydroxy group ortho to the azogroup, a metallized derivative thereof; (II) a monoazo or disazo dye ofthe formula

wherein: Het is an optionally substituted aromatic heterocyclic reactiveor non-reactive group or a reactive or non-reactive group having analiphatic chain; R³ or each R³, independently, is a chlorine atom, amethyl group, a methoxy group, a sulphonic acid group or a salt thereof,or is an amino group of the formula

in which each of R¹⁸ and R¹⁹, independently, is hydrogen, chloro,methyl, (C₁₋₄ alkyl)carbonyl, aminocarbonyl, vinylsulphonyl or a groupSO₂CH₂CH₂Q¹, in which Q¹ is as defined above; R⁴, or each R⁴independently, is hydrogen , a sulphonic acid group or a salt thereof, aC₁₋₈ alkyl group, a C₁₋₄ alkoxy group, a vinyl sulphonyl group or agroup SO₂CH₂CH₂Q² in which Q² is a leaving group removable underalkaline conditions to provide a vinyl sulphonyl group, which C₁₋₄ alkylgroup or C₁₋₄ alkyl moiety of the C₁₋₄ alkoxy group is optionallyinterrupted by an oxygen atom to provide an ether group and isoptionally substituted by a vinyl sulphonyl group or a groupSO₂CH₂CH₂Q², in which Q² is as defined above; or R⁴ (or when q is 2,each R⁴ independently) is a phenyl group optionally substituted by atleast one sulphonic acid group or a salt thereof or at least one groupHet, where Het is as defined above; or R⁴ is a group Het, where Het isas defined above; R⁵ is an aryl group selected from phenyl and naphthylgroups each optionally substituted by at least one sulphonic acid groupor a salt thereof or at least one group Het, as defined above; R²⁰ is ahydrogen atom or a C₁₋₄ alkyl group; R²¹ is a hydrogen atom, a C₁₋₄alkyl group, a sulphonic acid-C₁₋₄ alkyl group, achloroalkylsulphonyl-C₁₋₄ alkyl group or a group Het, where Het is asdefined above; m is 1 or 2; p is zero, 1 or 2; q is zero, 1 or 2; eachof w₁ and w₂ is zero or 1; and w₃ is 1, 2 or 3; and when p is zero, q iszero; at least one of R⁴, R⁵, R¹⁸, R¹⁹, R²¹ and Het being, or havingthereon at least one substituent which is, reactive; (III) amonoazopyridone dye of the formula

 wherein: each of R⁴⁰, R⁴¹, L¹ and L² is as defined above; R⁷ isoptionally present and is a cyano group or the group —CH₂SO₃H or thegroup —C(═O)NH₂; each of R²⁴ and R²⁵, independently, is a hydrogen atom,a C₁₋₄ alkyl group, a sulpho-C₁₋₄ alkyl group, or a carboxyl group; n is1 or 2; r is zero or 1; and each of s₁ and s₂ is zero or 1; and when R⁴⁰is a phenyl or naphthyl group S₂ is 1; at least one of R⁴⁰ and R⁴¹being, or having thereon at least one substituent which is, reactive;(IV) a monoazonaphthyl dye of the formula

 wherein: each of R¹, R⁴⁰, R⁴¹, L¹, L², x, y and z is as defined above;R⁹ is CH₃(C═O)—, Het (as defined above) or an aryl group selected fromphenyl and naphthyl, which Het or aryl group is optionally substitutedby at least one substituent, the or each substituent, independently,being selected from a sulphonic acid group and a salt thereof, a C₁₋₄alkyl group, a C₁₋₄ alkoxy group, a hydroxy group, an amino groupoptionally substituted by at least one methyl or sulphato group, a vinylsulphonyl group and a group SO₂CH₂CH₂Q¹ in which Q¹ is as defined above;R³⁵ is a C₁₋₄ alkyl or C₂₋₄ alkenyl group, which C₁₋₄ alkyl or C₂₋₄alkenyl group is optionally substituted by at least one halogen atom, asulphonic acid group or salt thereof, a chloroalkylsulphonyl group, avinylsulphonyl group or —SO₂CH₂CH₂Q¹, where Q¹ is as defined above andwhich C₁₋₄ alkyl or C₂₋₄ alkenyl group optionally additionally containsat least one oxygen or sulphur atom in the chain thereof; the group Het(as defined above); or an aryl group selected from phenyl and naphthyl,which Het or aryl group is optionally substituted by at least onesubstituent, the substituent or each substituent independently, beingselected from a sulphonic acid group and a salt thereof, a C₁₋₄ alkylgroup, a C₁₋₄ alkoxy group, a halogen atom, a hydroxy group, an aminogroup optionally substituted,by at least one methyl or sulphato group, avinylsulphonyl group, a vinylsulphonyloxyethyl group and a groupSO₂CH₂CH₂Q¹ in which Q¹ is as defined above; R⁵⁰ is a vinylsulphonylgroup or a group SO₂CH₂CH₂Q¹ (in which Q¹ is as defined above); at leastone of R¹, R⁹, R35, R⁴⁰, R⁴¹ and R⁵⁰ is, or has thereon at least onesubstituent which is, reactive; L³ is a linking group selected fromN(R²⁰), in which R²⁰ is as defined above; CO; COO; NHCO; NHCONH; SO₂NHand SO₂; L⁴ is a linking group selected from N(R²¹), in which R²¹ is asdefined above, CO, COO, NHCO, NHCONH, SO₂NH and SO₂; Z is hydroxy, aminoor methylamino; a is zero or 1-4; b is zero or 1-3; c is zero or 1; d iszero, 1 or 2; e is zero or 1; and when each of R¹ and Z provides ahydroxyl group ortho to the azo group, a metallized derivative thereof;(V) a disazoaminonaphthyl dye of the formula

 wherein: each of R¹ ₁R⁴⁰, R⁴¹, L¹, L², x, y and z is as defined above;each of V and W, independently, is NH₂ or OH; R¹⁴ is an aryl groupselected from phenyl and naphthyl groups optionally having at least onesubstituent thereon, the substituents, or each substituentindependently, being selected from a sulphonic acid group and a saltthereof, a C₁₋₄ alkyl group, a C₁₋₄ alkoxy group, a hydroxy group, avinyl sulphonyl group, a group SO₂CH₂CH₂Q¹ in which Q¹ is a leavinggroup removable under alkaline conditions to provide a vinyl sulphonylgroup; each of R⁵¹ and R⁵² independently is an aryl group selected fromphenyl and naphthyl groups each of which is optionally substituted by avinyl sulphonyl group, a group SO₂CH₂CH₂Q¹ in which Q¹ is a leavinggroup removable under alkaline conditions to provide a vinyl sulphonylgroup, or the group Het³, where Het³ is an optionally substitutedaromatic heterocyclic reactive group or a reactive group having analiphatic chain; each of L³ and L⁴, independently, is a linking groupselected from N(R²⁰), in which R²⁰ is hydrogen or C₁₋₄ alkyl; C(═O);C(═O)—O; S(═O)₂; S(═O)—NH; C(═O)—NH; and NHC(═O)NH; each of f, g and h,independently is zero or 1; and at least one of R¹, R⁴⁰, R⁴¹, R⁵¹ andR⁵² is, or has thereon at least one substituent which is, reactive; (VI)a formazan dye of the formula

 wherein: each of R¹⁶ and R¹⁷ independently of one another, each R¹⁶independently of one another and each R¹⁷ independently of one another,is a sulphonic acid group or a salt thereof, a vinyl sulphonyl group ora group SO₂CH₂CH₂Q¹ in which Q¹ is a leaving group removable underalkaline conditions to provide a vinyl sulphonyl group; each of Het¹ andHet², independently, is an optionally substituted aromatic heterocyclicreactive or non-reactive group or a reactive or non-reactive grouphaving an aliphatic chain; and each of R⁶⁰ and R⁶¹, independently, is anaryl group selected from phenyl and naphthyl groups each of which isoptionally substituted by a sulphonic acid group or a salt thereof, avinylsulphonyl group or a group SO₂CH₂CH₂Q¹ in which Q¹ is as definedabove; X¹ is a sulphonic acid group or a salt thereof or halogen; eachof i, j and v, independently, is zero, 1 or 2; and each of k, l, t andu, independently, is zero or 1; and at least one of R¹⁶, R¹⁷, R⁵⁰, R⁵¹,Het¹ and Het² is, or has thereon at least one substituent which is,reactive; (VII) a dye of the formula

 wherein: each of R¹, R², R³, R⁴, R²⁰, R²¹, R⁴⁰, L¹ Het, x, p, q, w₁, w₂and w₃ is as defined above; and at least one of R¹, R², R³, R⁴, R²¹, R⁴⁰and Het is, or has thereon at least one substituent which is, reactive;(VIII) a disazo dye of the formula

 wherein R⁵⁵ is an aryl group selected from phenyl and naphthyl groups;R⁵⁶ is a sulphonic acid group or a salt thereof or a reactive groupselected from a vinyl sulphonyl group and a group SO₂CH₂CH₂Q¹ in whichQ¹ is a leaving group removable under alkaline conditions to provide avinyl sulphonyl group; R⁵⁷ is an amino group or a group NHR^(A) in whichR^(A) is a C₁₋₄ alkyl group; R⁵⁸ is a sulphonic acid group or a saltthereof; R⁵⁹ is a sulphonic acid group or a salt thereof, a reactivegroup selected from a vinyl sulphonyl group and a group SO₂CH₂CH₂Q² inwinch Q² is a leaving group removable under alkaline conditions toprovide a vinyl sulphonyl group; or the group R⁵⁹ is a group Het or agroup L¹⁰-Het, where Het is an optionally substituted aromaticheterocyclic reactive or non-reactive group; R⁶⁵ is a ureido group or agroup HNC(═O)R^(B) in which R^(B) is a C₁₋₄ alkyl group; L¹⁰ is alinking group selected from N(R²⁰), in which R²⁰ is hydrogen or C₁₋₄alkyl; C(═O); C(═O)—O; S(═O)₂; S(═O)—NH; C(═O)—NH; and NHC(═O) NH; y₁ iszero, 1, 2 or 3; y² is zero, 1 or 2; y₃ is zero or 1; and y₄ is zero or1; and at least one of R⁵⁶ and R⁵⁹ is a reactive group; (IX) a dye ofthe formula

(X) a metal phthalocyanine dye of the formula

 wherein: MPc is a metallophthalocyanine chromophore; each of R⁷⁰ andR⁷¹, independently, is hydrogen or C₁₋₄ alkyl; B is a hydrocarbonbridging group; Het is a reactive heterocyclic group; each of x₁, x₂ andx₃ is a respective average value; x₁+x₂+x₃=4; x₁ is at least 1 x₂ iszero or 1; and x₃ is at least 1; and (XI) a triphenodioxazine dye of theformula (XI) (or a salt thereof)

 wherein: each of B¹ and B², independently, is a hydrocarbon bridginggroup; U¹ is H or SO₃H; and each of T¹ and T², independently, is halo,C₁₋₄ alkyl, or C₁₋₄ alkoxy; each of R⁸⁰ and R⁸¹ is a phenyl groupsubstituted by at least one sulphonic acid group or a salt thereof; eachof Het¹ and Het² is as defined above; and at least one of Het¹ and Het²is a reactive group.
 2. A dye mixture according to claim 1, wherein, inthe dye of the formula (A), at least one of Y¹ and Y² is the group—CH₂CH₂Q and Q is selected from chlorine, bromine, C₁₋₄-alkylsulfonyl,phenylsulfonyl, OSO₃H, SSO₃H, OP(O) (OH)₂, C₁₋₄-alkylsulfonyloxy,phenylsulfonyloxy, (C₁₋₄ alkyl) carbonyloxy, (C₁₋₄ dialkyl) amino or aradical of the formula

where Z⁹, Z¹⁰ and Z¹¹ are identical or different and are each,independently of one another, C₁₋₄ alkyl or benzyl and An^(θ) is in eachcase one equivalent of an anion.
 3. A dye mixture according to claim 2,in which, in the reactive dye of the formula (A), each of Y¹ and Y² isthe group HO₃SOCH₂CH₂.
 4. A dye mixture according to any precedingclaim, wherein the reactive dye (B) contains a group Het, where Het isan optionally substituted aromatic heterocyclic reactive group derivedfrom a halogen-substituted heterocyclic compound selected from1,3,5-triazine, quinoxaline, phthalazine, pyrimidine, pyridazine and2-(C₁₋₄ alkylsulphonyl) benzothiazole.
 5. A dye mixture according toclaim 4, wherein the aromatic heterocyclic reactive group is substitutedand at least one substituent is a halogen atom.
 6. A dye mixtureaccording to any one of claims 1 to 3, wherein the reactive dye (B)contains a group Het, where Het is a reactive group having an aliphaticchain and selected from acryloyl, mono-, di- or trichloroacryloyl,mono-, di- or tri- bromoacryloyl, —CO—CCl═CH—COOH, —CO—CH═CCl—COOH,2-chloropropionyl, 1,2-dichloropropionyl, 1,2-dibromopropionyl,3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl,2-sulfatoethylaminosulfonyl, 2-chloro-2,3,3-trifluorocyclobutylcarbonyl,2,2,3,3-tetrafluorocyclobutylcarbonyl,2,2,3,3-tetrafluorocyclobutylsulfonyl,2-(2,2,3,3-tetrafluorocyclobutyl)acryloyl, 1- or 2-alkyl- or 1- or2-arylsulfonylacryloyl, or a radical of the formula SO₂—Y³, SO₂NH—Y³,CONH—L⁶—SO₂—Y³ or NHCONH—L⁶—SO₂—Y³ where L⁶ is C₁-C₄-alkylene orphenylene and Y³ is a vinyl group or a group of the formula CH₂CH₂Q³ inwhich Q³ is a leaving group removable under alkaline conditions toprovide a vinyl group.
 7. A dye mixture according to any precedingclaim, wherein the reactive dye (B) has at least one of the groups Q¹and Q² therein and the or each of groups Q¹ and Q² independently isselected from chlorine, bromine, C₁₋₄-alkylsulfonyl, phenylsulfonyl,OSO₃H, SSO₃H, OP(O)(OH)₂, C₁₋₄-alkylsulfonyloxy, phenylsulfonyloxy,(C₁₋₄ alkyl) carbonyloxy, (C₁₋₄ dialkyl)amino or a radical of theformula

where Z⁹, Z¹⁰ and Z¹¹ are identical or different and are each,independently of one another, C₁₋₄-alkyl or benzyl and An^(θ) is in eachcase one equivalent of an anion.
 8. A dye mixture according to anypreceding claim, wherein the reactive dye (B) is a monoazopyrazole dyeof the formula (I), given and defined in claim
 1. 9. A dye mixtureaccording to claim 8, wherein, in the reactive dye (B) of the formula(I), at least one of the group [(R⁴¹—L²)_(z)(R⁴⁰—L¹)_(y)]R¹ and thegroup R² has a group —SO₂CH₂SO₂Q² substituted thereon, Q² being asdefined in claim
 1. 10. A dye mixture according to claim 8 or claim 9,wherein, in the reactive dye (B) Of the formula (I), x is zero and thegroup R¹ is substituted by at least one of a sulphonic acid group andthe group —SO₂CH₂SO₂Q¹, wherein Q¹ is as defined in claim
 1. 11. A dyemixture according to claim 8 or claim 9, wherein, in the reactive dye(B) of the formula (I), each of x, y and z is 1, each of L¹ and L² isNH, R⁴⁰ is the group Het, where Het is a triazine ring substituted by ahalogen atom and R⁴¹ is an optionally substituted phenyl group.
 12. Adye mixture according to claim 8 or claim 9, wherein, in the reactivedye (B) of the formula (I), each of x and z is 1, y is zero, L² is NHand R⁴¹ is the group Het, where Het is a difluorochloropyrimidinylgroup.
 13. A dye mixture according to claim 8 or claim 9, wherein, inthe reactive dye (B) of the formula (I), each of x and z is 1, y iszero, L² CONH (in which the nitrogen atom is attached to the group R¹and the carbon to the group R⁴¹) and R⁴¹ is the group Het, where Het isa 2,3-dichloroquinoxaline group.
 14. A dye mixture according to any oneof claims 8 to 13, wherein, in the reactive dye (B) of the formula (I),R² is a phenyl or naphthyl group substituted by at least one of asulphonic acid group and the group —SO₂CH₂SO₂Q², where Q² is as definedin claim
 1. 15. A dye mixture according to any one of claims 8 to 13,wherein, in the reactive dye (B) of the formula (I), R² is a phenyl ornaphthyl group substituted at least by the group NH-Het, where Het is atriazine ring substituted by a halogen atom and optionally substitutedby the group


16. A dye mixture according to any one of claims 8 to 15, wherein, inthe reactive dye, (B) of the formula (I), the group R¹ is substituted bya hydroxy group ortho to the azo group and the reactive dye (B) is inthe form of a copper complex.
 17. A dye mixture according to any one ofclaims 1 to 7, wherein the reactive dye (B) is monoazo or disazo dye, ofthe formula (II), given and defined in claim
 1. 18. A dye mixtureaccording to claim 17, wherein, in the reactive dye (B) of the formula(II), the group R⁵ is an aryl group selected from phenyl and naphthylgroups each substituted by at least one sulphonic acid group or a saltthereof or by a group Het, wherein Het is a vinylsulphonyl group or agroup SO₂CH₂CH₂Q¹ in which Q¹ is as defined in claim
 1. 19. A dyemixture according to claim 16 or claim 18, wherein, in the reactive dye(B) of the formula (II), m is 1, which dye is a monoazo dye.
 20. A dyemixture according to claim 19, wherein, in the reactive dye (B) of theformula (II), each of w₁, w₂, p and q is zero, w₃ is at least 2, atleast one of the groups R³ is a sulphonic acid group and the group R⁵ isan aryl group selected from phenyl and naphthyl groups each substitutedby a vinylsulphonyl group or a group —SO₂CH₂CH₂Q¹, where Q¹ is asdefined in claim
 1. 21. A dye mixture according to claim 19, wherein, inthe reactive dye (B) of the formula (II), each of w₁ and w₂ is zero,each of p and q is 1, R²¹ is hydrogen and R⁴ is selected from a triazinering substituted by at least one halogen atom and optionallyadditionally substituted by an amino group; and a pyrimidine groupsubstituted by at least one halogen atom and optionally additionallysubstituted by a methyl group.
 22. A dye mixture according to claim 19,wherein, in the reactive dye (B) of the formula (II), each of w₁, w₂, pand q is 1, R²⁰ is hydrogen, Het is a triazine ring substituted by ahalogen atom, R²¹ is hydrogen an R⁴ is selected from a phenyl group or agroup —SO₂CH₂CH₂Q¹, where Q¹ is as defined in claim 1, and a straight orbranched C₂₋₄ alkylene chain substituted by a substituent selected froma hydroxyl group; a sulphonic acid group or salt thereof; avinylsulphonyl group, a group —SO₂CH₂CH₂Q² ₁ where Q² is as defined inclaim 1; and a pyrimidinylamino group in which the pyrimidinyl group issubstituted by at least one halogen atom and optionally additionally bya methyl group; and which straight or branched C₂₋₄ alkylene groupoptionally contains a hetero atom selected from O, S and N(H).
 23. A dyemixture according to claim 19, wherein, in the reactive dye (B) of theformula (II), each of w₁ and w₂ is zero, each of p and q is 1 and eachof R²¹ and R⁴ is the group OSO₃H.
 24. A dye mixture according to claim19, wherein, in the reactive dye (B) of the formula (II), w₁ is zero,w₂is 1, p is 1, q is 1 R²¹ is hydrogen, R⁴ is a pyrimidinyl groupsubstituted by at least one halogen atom and optionally additionallysubstituted by a methyl group and Het is a non-reactive heterocyclicgroup of the formula


25. A dye mixture according to claim 19, which contains a dye of theformula (44)


26. A dye mixture according to any one of claims 1 to 7, wherein thereactive dye (B), is a monoazopyridone dye of the formula (III), givenand defined in claim
 1. 27. A dye according to claim 26, wherein, in thereactive dye (B) of the formula (III), each of r, s₁ and s₂ is 1, eachof L¹ and L² is NH, R⁴⁰ is a triazine ring substituted by a halogen atomand R⁴¹ is selected from a phenyl group substituted by at least one of achlorine atom, a sulphonic acid group or a salt thereof, avinylsulphonyl group or a group —SO₂CH₂CH₂Q¹, where Q¹ is as defined inclaim 1; and a straight or branched chain C₂₋₄ alkylene group optionallycontaining at least one oxygen atom and substituted by a vinylsulphonylgroup or a group —SO₂CH₂CH₂Q¹, where Q¹ is as defined in claim
 1. 28. Adye mixture according to claim 26, wherein, in the reactive dye (B) ofthe formula (III), each of r and s₁ is 1, s₂ is zero, L² is NH, R⁴¹ is apyrimidinyl group substituted by at least one halogen atom andoptionally additionally substituted by a methyl group and R⁴⁰ is anaphtho-(1,2-d)-1,2,3-triazole substituted by at least one sulphonicacid group or salt thereof.
 29. A dye mixture according to claim 26,wherein, in the reactive dye (B) of the formula (III), each of r₁, s₁and s₂ is 1, L¹ is CONH (in which the carbon atom is attached to thegroup R⁴⁰), L² is NH, R⁴⁰ is an optionally substituted phenyl group andR⁴¹ is a pyrimidinyl group substituted by at least one halogen atom andoptionally additionally substituted by a methyl group.
 30. A dye mixtureaccording to any one of claims 1 to 7, wherein the reactive dye (B) is amonoazonaphthyl dye of the formula (IV), given and defined in claim 1.31. A dye mixture according to claim 30, wherein, in the reactive dye(B) ok the formula (IV), x is zero, d is 1 and a or b is
 1. 32. A dyemixture according to claim 31, wherein e is zero.
 33. A dye mixtureaccording to claim 30, wherein, in the reactive dye (B) of the formula,x is 1, y is zero, z is 1, L² is NH and R⁴¹ is a pyrimidinyl groupsubstituted by at least one halogen atom and optionally additionallysubstituted by a methyl group.
 34. A dye mixture according to claim 30,wherein, in the reactive dye (B) of the formula (IV), x is 1, y is zero,Z is 1, L² is CONH (with the carbon atom attached to the group R¹ andthe nitrogen atom to the group R⁴¹) and R⁴¹ is a phenyl groupsubstituted by a vinylsulphonyl group or a group —SO₂CH₂CH₂Q¹, where Q¹is as defined in claim
 1. 35. A dye mixture according to claim 30,wherein, in the reactive dye (B) of the formula (IV) each of x, y and zis 1, each of L¹and L² is NH, R⁴⁰ is a triazine ring substituted by ahalogen atom and R⁴¹ is an aromatic group selected from phenyl andnaphthyl groups each substituted by at least one of a sulphonic acidgroup or a salt thereof, a vinylsulphonyl group and the group—SO₂CH₂CH₂Q¹, where Q¹ is as defined in claim
 1. 36. A dye mixtureaccording to any one of claims 33 to 35, wherein e is zero.
 37. A dyemixture according to claim 30, wherein, in the reactive dye (B) of theformula (IV), e is 1, c is zero, L³ is CONH (where either the nitrogenor carbon atom thereof is attached to the group R⁹) and R⁹ is a methylgroup.
 38. A dye mixture according to claim 30, wherein, in the reactivedye (B) of the formula (IV), e is 1, c is zero, L³ is CONH (where eitherthe nitrogen or carbon atom thereof is attached to the group R⁹) and R⁹is a phenyl group optionally substituted by at least one substituent,the or each substituent being selected from methoxy, carboxyethyl,sulphoethyl, carboxyethenyl, 1,2-dibromoalkyl, chloroethylsulphonyl,vinylsulphonyl, a group of the formula —SO₂CH₂CH₂Q¹ where Q¹ is asdefined in claim 1 and a 2,3-dichloroquinoxaline group.
 39. A dyemixture according to claim 30, wherein, in the reactive dye (B) of theformula (IV), e is 1, c is 1, L³ is CONH (where either the nitrogen orcarbon atom thereof is attached to the group R⁹), R⁹ is a phenyl groupsubstituted at least by the group L⁴—R³⁵, where L⁴ is NH and R³⁵ is avinyl group optionally substituted by a halogen atom or a pyrimidinylgroup substituted by a halogen atom and optionally additionallysubstituted by a methyl group.
 40. A dye mixture according to claim 30,wherein, in the reactive dye (B) of the formula (IV), e is 1, c is zero,L¹ is N(R²⁰), where R²⁰ is as defined in claim 1 and R⁹ is avinylsulphonyl group, a group —SO₂CH₂CH₂Q¹ wherein Q¹ is as defined inclaim 1, or a pyrimidinyl group substituted by a halogen atom andoptionally additionally substituted by a methyl group.
 41. A dye mixtureaccording to claim 40, wherein, in the group N(R²⁰), R²⁰ is a halogenatom or a methyl group.
 42. A dye mixture according to claim 30,wherein, in the reactive dye (B) of the formula (IV), e is 1, c is zero,L³ is N(R²⁰), where R²⁰ is as defined in claim 1 and R⁹ is a triazinering substituted by at least one halogen atom.
 43. A dye mixtureaccording to claim 42, wherein the triazine ring is substituted by twohalogen atoms.
 44. A dye mixture according to claim 42, wherein thetriazine ring is substituted by one halogen atom and a morpholinylgroup.
 45. A dye mixture according to claim 30, wherein, in the reactivedye (B) of the formula (IV), e is 1, c is 1, L³ is N(R²⁰), where R²⁰ isas defined in claim 1, L⁴ is the group R²¹, where R²¹ is as defined inclaim 1 and R³⁵ is selected from a phenyl group optionally substitutedby a sulphonic acid group or salt thereof, a halogen atom, avinylsulphonyloxyalkyl group, a vinylsulphonyl group or the group—SO₂CH₂CH₂Q¹, where Q¹ is as defined in claim 1; and a C₁₋₄ alkyl groupoptionally substituted by a vinylsulphonyl group, the group—SO₂CH₂CH₂Q¹, where Q¹ is as defined in claim 1, a sulphonic acid groupor a salt thereof or a chloroalkylsulphonyl group, which C₁₋₄ alkylgroup-optionally additionally contains at least one oxygen or sulphuratom in the chain thereof.
 46. A dye mixture according to any one ofclaims 37 to 45, wherein x is zero.
 47. A dye mixture according to anyone of claims 30 to 46, wherein, in the reactive dye (B) of the formula(IV), each of the groups R¹ and the naphthalene nucleus is substitutedby a respective hydroxyl group ortho to the azo group and the reactivedye (B) is in the form of a copper complex thereof.
 48. A dye mixtureaccording to claim 30, which contains a dye of the formula (53)


49. A dye mixture according to any one of claims 1 to 7, wherein thereactive dye (B) is a disazo dye of the formula (V), given and definedin claim
 1. 50. A dye mixture according to claim 49, wherein, in thereactive dye (B) of the formula (V), V is amino, W is hydroxy, each ofR¹ and R¹⁴ is a phenyl group substituted by at least one substituent,the or each substituent independently being selected from a sulphonicacid group or a salt thereof, a vinylsulphonyl group and a groupSO₂CH₂CH₂Q¹, where Q¹ is as defined in claim 1 and R¹⁴ is optionallyadditionally substituted by at least one methoxy group.
 51. A dyemixture according to claim 49 or claim 50, wherein, in the reactive dye(B) of the formula (V), each of x and h is zero.
 52. A dye mixtureaccording to claim 49 or claim 50, wherein, in the reactive dye (B) ofthe formula (V), at least one of x and h is
 1. 53. A dye mixtureaccording to claim 52, wherein, each of x and h is
 1. 54. A dye mixtureaccording to claim 50, wherein each of x, y and z is 1, each of L¹ andL² is NH, R⁴⁰ is a triazine ring substituted by a halogen atom and R⁴¹is a phenyl group substituted by at least one substituent, the or eachsubstituent independently being selected from a sulphonic acid group ora salt thereof, a vinylsulphonyl group and a group SO₂CH₂CH₂Q¹, where Q¹is as defined in claim
 1. 55. A dye mixture according to any one ofclaim 50 and 52 to 54, wherein each of f, g and h is 1, each of L³ andL⁴ is NH, R⁵¹ is a triazine ring substituted by a halogen atom and R⁵²is a phenyl group substituted by at least one substituent the or eachsubstituent independently being selected from a halogen atom, asulphonic acid group or a salt thereof, a vinylsulphonyl group and agroup SO₂CH₂CH₂Q¹, where Q¹ is as defined in claim
 1. 56. A dye mixtureaccording to claim 49, wherein, in the reactive dye (B) of the formula(V), V is amino, W is hydroxy, h is zero and R¹⁴ is a naphthalene groupsubstituted by at least one sulphonic acid group.
 57. A dye mixtureaccording to claim 56, wherein each of x, y and z is 1, R¹ is a phenylgroup optionally substituted by a sulphonic acid group or a saltthereof, each of L¹ and L² is NH, R⁴⁰ is a triazine ring substituted bya halogen atom and R⁴¹ is a phenyl group substituted by at least onesubstituent, the or each substituent independently being selected from asulphonic acid group or a salt thereof, a vinylsulphonyl group and agroup SO₂CH₂CH₂Q¹, where Q¹ is as defined in claim
 1. 58. A dye mixtureaccording to claim 49, wherein, in the reactive dye (B) of the formula(V), V is amino, W is hydroxy, h is 1, f is zero, g is 1, L⁴ is NH andR⁵² is the group Het³, where Het³ is a substituted aromatic heterocyclicgroup.
 59. A dye mixture according to claim 58, wherein the group Het³is a pyrimidinyl group substituted by at least one halogen atom andoptionally additionally substituted by a methyl group.
 60. A dye mixtureaccording to claim 59, wherein x is zero and R¹ is a phenyl groupsubstituted by a vinylsulphonyl group or SO₂CH₂CH₂Q¹ ₁ where Q¹ is asdefined in claim
 1. 61. A dye mixture according to claim 49, wherein, inthe reactive dye (B) of the formula (V), V is amino, W is hydroxy, h is1, f is zero, g is 1, L¹ is NHCO (where either the nitrogen or carbonatom thereof is attached to the group R¹⁴) and R⁵² is the group Het³,where Het³ is a reactive group having an aliphatic chain.
 62. A dyemixture according to claim 61, wherein the group Het³ is avinylsulphonyl group or SO₂CH₂CH₂Q¹, where Q¹ is as defined in claim 1.63. A dye mixture according to claim 62, wherein x is zero and R¹ is aphenyl group substituted by a vinylsulphonyl group or SO₂CH₂CH₂Q¹, whereQ¹ is as defined in claim
 1. 64. A dye mixture according to claim 49,which contains a dye of the formula (105)


65. A dye mixture according to claim 64, which additionally contains adye of the formula (44)


66. A dye mixture according to claim 49, which contains a dye of theformula (163)


67. A dye mixture according to claim 49, which contains a dye of theformula (167)


68. A dye mixture according to claim 66 or 67, which contains each ofthe dyes of the formulae (163) and (167).
 69. A dye mixture according toany one of claims 1 to 7, wherein the reactive dye (B) is a formazan dyeof the formula (VI) given and defined in claim
 1. 70. A dye mixtureaccording to claim 69, wherein, in the reactive dye (B) of the formula(VI), each of u and v is zero, i is 1, R¹⁶ is a sulphonic acid group ora salt thereof, j is 2 and one R¹⁷ is a sulphonic acid group or a saltthereof and the other R¹⁷ is a vinylsulphonyl group or SO₂CH₂CH₂Q¹,where Q¹ is as defined in claim
 1. 71. A dye mixture according to claim69, wherein, in the reactive dye (B) of the formula (VI), v is zero, iis 1, R¹⁶ is a sulphonic acid group or a salt thereof, j is 1, R¹⁷ is asulphonic acid group, u is 1 and Het¹ is atriazine ring substituted by ahalogen atom.
 72. A dye mixture according to claim 71, wherein each of kand l is zero, t is 1 and R⁶¹ is a phenyl group substituted by at leastone sulphonic acid group or a salt thereof.
 73. A dye mixture accordingto claim 71, wherein each of k, l and t is 1, each of R⁶⁰ and R⁶¹independently is a phenyl group substituted by at least one sulphonicacid group or a salt thereof and Het² is a triazine ring substituted bya halogen atom.
 74. A dye mixture according to claim 71, wherein each ofk and t is zero, l is 1 and Het² is a reactive group having an aliphaticchain.
 75. A dye mixture according to any one of claims 1 to 7, whereinthe reactive dye (B) is a disazo dye of the formula (VIII), given anddefined in claim
 1. 76. A dye mixture according to claim 75, wherein R⁵⁵is a naphthyl group; R⁵⁶ is a sulphonic acid group or a salt thereof;R⁵⁹ is a group L¹⁰-Het, where L¹⁰ is the group N(H)— and Het is areactive heterocyclic group substituted by at least one halogen atom; y₁is 1, 2 or 3; and each of y², y₃ and y₄ is zero.
 77. A dye of theformula


78. A dye mixture according to claim 75, wherein R⁵⁵ is a phenyl group;the group R⁵⁶ or each group R⁵⁶ independently is a sulphonic acid groupor a salt thereof or is a reactive group selected from a vinyl sulphonylgroup and a group SO₂CH₂CH₂Q² in which Q² is as defined in claim 1; y₁is 1 or 2; and, at least one group R⁵⁶ is a said reactive group or thegroup R⁵⁹ is or includes a reactive group.
 79. A dye mixture accordingto claim 78, wherein at least one group R⁵⁶ or the group R⁵⁹ is areactive group selected from a vinyl sulphonyl group and a groupSO₂CH₂CH₂Q¹ in which Q¹ is as defined in claim
 1. 80. A dye mixtureaccording to claim 78, wherein at least one group R⁵⁶ is a sulphonicacid group or a salt thereof and R⁵⁹ is the group L¹⁰-Het, where L¹⁰ isthe group N(H)— and Het is a reactive triazine group substituted by ahalogen atom and additionally, by the group NHCH₂CH₂SO₃H.
 81. A disazodye of the formula


82. A disazo dye of the formula


83. A dye mixture according to any one of claims 1 to 7, wherein thereactive dye (B) is a phthalocyanine dye of the formula (X), given anddefined in claim
 1. 84. A dye mixture according to claim 83, wherein, inthe reactive dye (B) of the formula (X), respective average values ofx₁, x₂ and x₃ are x₁ is 3, x₂ is zero and x₃ is 1, three of the fourisoindole rings of the phthalocyanine have a respective sulphonic acidsubstituent (or a salt thereof) thereon and the other isoindole ring hasa group SO₂NH—B—NH—Het substituted thereon.
 85. A dye mixture accordingto claim 84, wherein B is a straight or branched C₂₋₄ alkylene group andHet is a triazine ring substituted by at least one halogen atom andoptionally additionally substituted by a methoxy group.
 86. A dyemixture according to any one of claims 1 to 7, wherein the reactive dye(B) is a triphendioxazine dye of the formula (XI), given and defined inclaim 1, or a salt thereof.
 87. A dye mixture according to claim 86,wherein, in the reactive dye (B) of the formula (XI), each of T¹ and T²is a halogen atom, each U¹ is a sulphonic acid group or a salt thereof,each of B¹ and B² independently is a straight or branched C₂₋₄ alkylenegroup, each of Het¹ and Het² independently is a triazine ringsubstituted by a halogen atom and each of R⁸⁰ and R⁸¹ independently is aphenyl group substituted by at least one sulphonic acid group or a saltthereof.
 88. A dye mixture according to any preceding claim comprising,by weight of the total weight of the dyes, from 10 to 99.5% by weight,inclusive of component (A), given and defined above, and from 0.5 to 90%by weight, inclusive of component (B), given and defined in claim 1.